Hydration of olefins



Patented Nov. 11, 19752 UNITED STATES PATENT `OFli'lClE'.

HYDRTON 0F ULEFINS Josphn. Woodbridge, Pensauken, N. JA., assigner to The Atlantic :Refining Company, Philadeb .phia, Pay., a corporation roi Pennsylvania Naim-wing. viipilfieationfi"e'bruary 21,1950,

serial No. 145,589

sion of oleiin'sinto alcohols, and relates iino're haifj'ics'u'larlyh to the hydration Joff valipl'ia'tic monovIn *accordance v"With this invention, "an olefin containing from 2 to carbon -atq'rln's is contac't'edjvi'th an `aqrn'eous l`si'llition of LBF; having Lafspeciic `gravitybetween51.65 and 1.7- at 25 C Vyandliq'u-eried SO; `at `a temperaturebetween n-T-ZESWCL 'and 50 fora period of time suff- ''cient Lito effect hydration of the -oleliln vto vthe corresponding alcohol. Aiter conversion, the alci'roi is separateffrem the reaetan-; :mixture land unconverted wenn 'may-be recycled for further treatment.

""rhe 7cleans which may be employed are prefe'ijably primary, 'and 'seco'n'clay oleiihs including ethylene'. propylene, :bute'ne-l, butene2,"and the higher homologous r'jrim-"ary 'and secondary pentenes, hex'enes, heptenes, "n'onnes, decenes, and 'the like. 'The aliphatic cyclo-olens 'such as iylp'entene, c'yclohexene, cycloheptene cyclooteiiefan'dfthe alkyl cyclo-oleins inwhich the double-pone is 1not adjacent fthe `ea-norm latom tearing"th-e'aikyigmip are also suite-bie for'ukse.

vThe 1liiy'iaa.ting agent comprising an "aqueous 'solution "of BFa Ais prepared by passing gaseous hito cooled Water v"i'i'rwitil' the specific 7'gnravity solution fausjwthin 'the range-of 15,65 "and 1.75 "a't 25? Solutions having ia specific gravity above 1.75 are undesirable ,since they 'convert the 'olefin 'to l'polymers at the Mexpense of hydration. Ilor example, *solutions having a specific gravity of 1.79-1.80 give mostly olefin polymer 'Withlittl'e or 'no alcohol. On the other hand, solutions having -a specific gravity below 1.6`5, for example, '1.60, ar'etoodilute tobe satisfactory, since at low temperatures '(--50 C. to -18 C.) ice will form to an undesirable extent, whilefa't higher temperatures `(25" C.) the solution will be inactive due to its high water content. Therefore, it is 'essential to maintain ltlie'faqieoiis solution of BFa at'a 'gravity betwe'en 1g 5 ahd 1;'75 foruseund'r the hydrati'onfcononsoil'fthisinvention. The weight ratio 'of fa' ueus "BFa 'solution 'to ble''n may range 'betwn'il vand`2.0 to `1, olep'endiiig upon-the 'nae 'ofthe oleiin, "the hydration temperature, the eiiciency of contacting'and the amount 'of S02 employed. In general, about 1 part by Weight of BFa solution to 1 part by weight of olefin is satisfactory, the only requirement being that suilcient Water is present to hydrate a substantial proportion of the olefin.

The sulfur dioxide (SO2) employed in conjunction with the aqueous solution of BF3 funcaolairms. (oi. 260.631.)

. .2 separation, Si. e., unreacted 'olefin (and traces of polymer); liquid Soiand alcohol; and-aqueous BFS saturated .with SO2. The Weight ratio of SO2 to oleiinimafy:rangebetween 0.05.and 5to 1, equal Weights 'being satisfactory .in-m^ost ycases andgiv- .ing rise to liquid phase separation `permitting ready Lrecovery .of the products and unreacted components, and 'recyclingof 'thelatten Thevhydration'operation is preferably carriedout under conditions in Vwhich `all fof .the components-'are substantially in 'the liquid phase, and in some cases, 'this will require a closeclisystem. operating under su'p'eratniosph'eric pressure The present invention .may befurther illusi traten .by "the .e following examples, which,.;now

ever, are fn'o'tito be fconstruedfas limiting the scope thereof.

Hydration icatalysts were Amade up 'by passing gaseous :B'Fa through cooledwater until the -r def'si-red gra'vity was attained. l1'00 ,gmini the aqueous solution Sof B173 'was :then .added lslowly-'to ll'fllgmrof liquid ISOAzfa't h-34" t0.. .a vessel 'provided with fa 'mechanical isti-rrer. :mo 'this in'iXtre W-as added, with Istirring, ..1 :mole of .the desired olefin. Thenrixture "was vigorouslyl'stirred for 3A 'to 4- hour's, lv/h'ile maintaining the temperature between -23-TC. and-48 C. The reaction mixture, upon completion ofthe v'stir'rir'ig was poured finto 75 Sgm. ofvaterfand falvlowefifto stratify 1in layers. The aqueous .BFs l'ayei' "Wa's y"dra'v'i/n off, 'fth'e SOzconta'n'ed therein 'thenfbe'ing "recovered -by Vaporization and `the V'remainin'g layer fcomp'rising "alcohol, '-unconv'erted Aolefin and traces 'of vpoly-mers, was washed `ii/a'ter and then lwith sodium Ycarbonate solution 'to'remove traces o'f-SOz. vOleiin andpolymerrremaining in the alcohol were separatedby ffra'ctionaldistillation. ARecycling oi f-the funco'nverted -len "substantial-ly increased l"the ultimate-yield of alcohol. The results 'fior the hydrationlobu- :tene-:72, -Yoctene-'L fand cyclohexene are tabulated below.

.. Alcohol-,Percent v SnGnoi v ydration 'Yield No. 'Oleiln 'lSFg-A-g'z period at 25 C. -(hours) @new Reep .throughn cllng 1.71 A1,.5 groe; lam 1. 73 0. 75 34. 4 l. 71 l1. 5 24.3 44. 2 l. 71 2. 0 35. 4 44. 6 1.68 3.0 47.3 1.71 4.0 45.4 48.7 7----. -do 1.71 l2.15 39.6 49.0 8 cyclohexene. 1.71 1.75 14.0 57.0 9 echelle-1--... 1.71 1.5 3.0 10 dO 1.73 l1.5 1.0

1 Contained n-pentane diluent in an amount equal to the octane-1. l Contained l the amount ofliquid SO2, i. e., 57 gm. i Contained no liquid S01, resulting in high conversion to polymers.

From the above data, it is apparent that sub- Vare converted almost completely to olefin polymers. Tertiary olens are not usually suitable for use in accordance with this invention, since they appearto be more readily polymerized than hydrated. Likewise, if the specific gravity of the aqueous solution of BFs is too high, i. e. above 1.75. the primary and secondary olefins tend to polymerize even in the presence of SO2. For example, octene-l treated with aqueous BFa, having a specific gravity of 1.79 at 25 C. and liquid SO2 at 23 C. to 18 C., was converted almost completely to octene polymers. However, with the catalysts and under the conditions specied herein, substantial yields of alcohols can be obtained from the primary and secondary olens. In some cases, it is desirable to dilute the oleiin with an inert solvent to lower the viscosity prior to and during the hydration reaction. Such solvents or diluents include liquefied propane, butane, pentane, hexane, petroleum ether, 88 petroleum naphtha, and similar inert essentially parainic hydrocarbons or mixtures thereof. The quantity of diluent .to be employed will depend upon the nature of the olefin and the hydration temperature, however, quantities of the order oi 0.25 to volumes of diluent per volume of olen may be used, equal volumes usually being satisfactory. The process of the present invention may be carried out batch-wise in suitable vessels such as stirring autoclaves, or continuously in vessels permitting withdrawal of a portion of the reactant mixture, separation of the resultant alcohol, and recycling of the catalyst and unconverted olefin. Following hydration, the reactants and products may be separated and recovered by decantation, fractional distillation, or other conventional methods.

I claim:A

1. A method for converting primary and 'secondary olefins intoan alcohol, which comprises contacting said olefin with an aqueous solution of BFS having a speciiic gravity between 1.65 and 1.75 at C. and liquefied SO2 at a reaction temperature of +25 C. to 50 C. the-weight ratio of SO2 to olefin being from 0.05 to 5:1, and recovering the resulting alcohol from the reactant mixture.

2. A method for converting primary and secondary olefins into an alcohol, which comprises contacting said olefin with an aqueous solution of BFa having a specific gravity between 1.65 and 1.75 at 25 C. and liqueed SO2 at a reaction temperature of +25 C. to 50 C., the weight ratio of aqueous BF3 to olefin being from 0.1 to 2:'1' and the weight ratio of SO2 to olefin being from 0.05 to 5:1, and recovering the resulting alcohol from the reactant mixture.

3. A method for converting primary and secondary oleiins into an alcohol, which comprises contacting said olefin, in the presence of an 4 inert, liquid parainic hydrocarbon diluent, with an aqueous solution of BF3 having va specific gravity between 1.65'and 1.75 at .25 C. and liquefied SO2 at a reactionternperature of +25 C. to 50 C., the weight ratio of aqueous BFa to olen being from 0.1 to 2:1 and the weight ratio of SO2 to olefin being from 0.05 to 5:1, and

recovering the resulting alcohol from the reactant mixture.

4. A method for converting an aliphatic monoolen containing from 2 to 20 carbon atoms into an alcohol, which comprises contacting said olefin with an aqueous solution of BFa, having a specic gravity between 1.65 and 1.75 at 25 C. and liquefied SO2 at a reaction temperature of +25 C. to 50 C., and recovering the resulting alcohol from the reactant mixture.

5. A method for converting an aliphatic monoolen containing from 2 to 20 carbon atoms into an alcohol, which comprises contacting said olefin with an aqueous solution of BFi having a specific gravity between 1.65- and 1.75 at 25 C. and liquefied SO2I at a reaction temperature of +25 C. to C., the weight ratio of aqueous BFa to olen being from 0.1 to 2:1 and the weight ratio of SO2,` to olen being from 0.05 to 5:1, and recovering the resulting alcohol from the reactant mixture.

6. A method for converting butene-2 into 2- butanol, which comprises' contacting butene-2 with an aqueous solution of BFs havinga specific gravity between 1.68 and 1.72 at 25 C. and liquefied SO2 at a reaction temperature of 30 C. to 18 C., and recovering the resulting 2- butanol from the reactant mixture.

7. A method for converting cyclohexene into cyclohexanol, which comprises contacting cyclohexene with an aqueous solution of BFa having a specific gravity between 1.68 and 1.72 at 25 C. and liquefied SO2 at a reaction temperature of 30 C. to 18 C., and recovering the resulting cyclohexanol from the reactant mixture.

8. A method for converting octene-1 into 2- octanol, which comprises contacting octene-l with an aqueous solution of BFa having a specic gravity between 1.68 and 1.72 at 25 C. and liqueed SO2 at a reaction temperature of 30 C. to 18 C., and recovering the resulting 2- octa-nol from the reactant mixture.

JOSEPH E. WOODBRIDGE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,014,740 Larson Sept. 19, 1935 2,135,455 Loder Nov.1, 1938 2,220,307 Whiteley, Jr. et al. ;Nov. 5, 1940 2,442,643 Elwell et al. June 1, 1948 2,442,644 Elwell et al. June 1, 1948 2,442,645 Elwell et al. June 1. 1948 2,457,882 Freyl Jan. 4, 1949 

1. A METHOD FOR CONVERTING PRIMARY AND SECONDARY OLEGFINS INTO AN ALCOHOL, WHICH COMPRISES CONTCTING SAID OLEFIN WITH AN AQUEOUS SOLUTION OF BF3 HAVING A SPECIFIC GRAVITY BETWEEN 1.65 AND 1.75 AT 25* C. AND LIQUIFIED SO2 AT A REACTION TEMPERATURE OF +25* C. TO -50* C. THE WEIGHT RATIO OF SO2 TO OLEFIN BEING FROM 0.05 TO 5:1, AND RECOVERING THE RESULTING ALCOHOL FROM THE REACTANT MIXTURE. 